Novel anti-reflection conductive film
Technical field
The present invention relates to a kind of attached to the anti-reflection conductive film on the transparent material, especially for liquid crystal display, cathode-ray tube (CRT), building glass, touch panel, screen wave filter etc. attached to the anti-reflection conductive film on optical glass and the transparent plastic substrate.
Background technology
When cathode-ray tube (CRT) or this class display device of LCD are used in outdoor bright public place, extraneous light has very large interference to display screen, especially some LCDs (LCD), human eye almost can not normally be differentiated display color colourity and contrast, make this class display can not bring into play display effect normally, almost can not see content displayed in the sun as the LCDs of mobile phone.
Head it off can adopt following two kinds of methods, and the first reduces the loss percentage (comprise the absorption and each interface that can't again utilize reflecting part to light of material itself) of each parts of display device light process to light; It two is to reduce the reflection of extraneous light on each interface, to strengthen the ratio that the light that sends from liquid crystal display enters human eye.Increasing antireflecting film on each interface is a kind of effective ways of head it off, and its principle is to utilize multilayer to have the rete of different refractivity and different-thickness, forms composite membrane according to certain arrangement regulation, forms interference of light, thereby eliminates reflection.
The a large amount of use of traditional optical anti film is used to eliminate the surface reflection of plastics or glass substrate on the plastics or glass substrate of camera lens surface, lens surface, optical element surface, liquid crystal display device, cathode-ray tube (CRT), building glass and touch-screen.The optical anti film is to utilize the interference of light principle, the individual layer anti-reflective film is when allowing two of rete upper and lower interface reflection restraint the optical path difference (being that optical thickness is 1/4 reference wavelength) of coherent rays generation 1/2, light generation destructive interference, reflected light is eliminated mutually, thereby reduces surface reflection.Antireflection multilayer film adopts high-index material (H) and low-index material (L) usually, as TiO
2And SiO
2, form the film layer structure that light is interfered mutually, different wavelength is produced interference disappear mutually, thereby reduction plastics or glass substrate are to the reflection of different wave length.Generally speaking, for common optical plastic and glass substrate, substrate is 1.52 o'clock in 550nm place refractive index, a reflection that surface of contact will produce 4%-4.5% of substrate and air, and two surface of contact will produce the reflection of 8%-9%.And behind the use anti-reflective film, the reflection on surface is reduced to below 1%.
In accordance with this principle, disclose multiple anti-reflection conductive film in the prior art, more representationally be:
U.S. Patent No. 5986796 and No.5825255 disclose a kind of antireflecting film layer structure, and wherein example adopts the optical thickness design of 1/4 reference wavelength, makes rete reach antireflecting effect.But this invention outermost layer has used when the wavelength of 550nm, and refractive index is 1.38 MgF
2As low-index material, so outermost material itself is non-conductive, can not satisfy the performance requirement of antireflection and conduction simultaneously.
Announced a kind of employing CeO in the U.S. Patent No. 4921760
2, Al
2O
3, ZrO
2, SiO
2, TiO
2, Ta
2O
5Design as material Deng oxide, outermost material is SiO in the example of announcing
2, the refractive index at the 550nm place is 1.46, the gross thickness of rete is 358.0nm.Same outermost material itself is non-conductive, can not satisfy the performance requirement of antireflection and conduction simultaneously.
U.S. Patent No. 5091244 and 5407733 has adopted TiN, NbN, SnO
2, SiO
2, Al
2O
3And Nb
2O
5Deng oxide and nitride design, the film layer structure of announcement is 4 layers, and gross thickness is 161.0nm, and outermost material is SiO2, and the refractive index at 550nm wavelength place is 1.46, the intensity of reflected light of visible light can only be reduced to 50%.Same outermost material itself is non-conductive, can not satisfy the performance requirement of antireflection and conduction simultaneously.
U.S. Patent No. 5728456 and 5783049 discloses a kind of sputtering method deposition anti-reflection film that adopts on plastic sheeting.Film material has adopted ITO, SiO
2And fluoride, rete is 6 layers of structure, and gross thickness is 363.0nm, and outermost layer is low-index material SiO
2, the refractive index at 550nm wavelength place is 1.46.Same outermost material itself is non-conductive, can not satisfy the performance requirement of antireflection and conduction simultaneously.
The Chinese patent publication number is CN1665753, has announced a kind of transparent base that comprises antireflection coatings.This transparent base has at least one deck to comprise the anti-dazzle coating that is made of lamination film, vertical direction at substrate, laminated material comprises successively: first rete have refractive index between 1.8-2.2 and its geometric thickness between 5-50nm, second rete has refractive index between 1.35-1.65, and geometric thickness is between 5-50nm, the tertiary membrane layer has optical refractive index between 1.8-2.2, and geometric thickness is between 40-150nm, the 4th rete has optical refractive index between 1.35-1.65, and geometric thickness is between 40-150nm.Same outermost material itself is non-conductive, can not satisfy the performance requirement of antireflection and conduction simultaneously.
The Chinese patent publication number is CN1280676A, has announced a kind of multilayer electrically conductive anti-reflective coating.Its invention has comprised to be coated on the multilayer inorganic anti-reflective coating with predetermined optical properties on the flexible parent metal.This coating is the lamination that five kinds of material layers are formed, wherein the 3rd layer (playing number from outside to inside) is by the conductive material empty layer that constitutes of indium-tin oxide preferably, this conductive material has the adjustable thin film resistance of about 25-2000 Ω/sq, thereby does not influence the optical property of coating.But same outermost material itself is non-conductive, also needs to add the technology of etching on technology, has therefore increased the instability of technology, and yields reduces.
U.S. Patent No. 6586101 discloses a kind of antireflective optical multilayer film, has five-layer structure, and by beginning to count ground floor, the second layer, the 3rd layer, the 4th layer and layer 5 from substrate layer farthest.It is SiO that this multilayered film material comprises ground floor, the material that material is ITO
2The second layer, material be the 3rd layer, the material material SiO of NbO
2The 4th layer and material be the layer 5 of NbO.This invention can solve combination transparent and conduction, is unsuitable for large tracts of land, in batches quantity-produced requirement but the thickness of the film layer structure complexity, the especially high refractive index layer that are to use is too thick.
Chinese patent publication number CN1389346A has announced a kind of antireflective optical multilayer film, and rete has five-layer structure, and is ground floor, the second layer, C grade, the 4th layer and layer 5 by beginning to have calculated from substrate layer farthest.It is SiO that this multilayer film comprises ground floor, the material that material is ITO
2The second layer, material be that the 3rd layer of NbO, material are SiO
2The 4th layer and material be the layer 5 of NbO.The film layer structure of having announced is as follows:
This film layer structure can be realized high transmittance, and when visible wavelength was 460nm-600nm, reflectivity can be lower than 0.1%.But because the light of each wavelength period is for the stimulation degree difference of human eyes, the light that eyes are worked is 530nm-570nm at wavelength, the light of other wave band to the stimulation of eyes with far away more weak more from 550nm, light intensity contribution to human eye is also far away more weak more, and visible light is seen Fig. 8 to the stimulation function of human eyes.Therefore to the optimal design of rete the time, can make full use of this feature reduction film layer structure and reduce thicknesses of layers.The thickness of high refractive index layer is up to 30nm-100nm among U.S. Patent No. 6586101 and the Chinese patent publication number CN1389346A, because high-index material is the difficult high deposition rate plated film of realizing in the technology of evaporation coating and sputter coating, the thicker difficulty that will increase technology of rete increases equipment and material cost simultaneously.
The Chinese patent publication number is CN1447133A, discloses a kind of reflection coating layer with electrically conducting transparent superficial layer.The rete of this invention has four-layer structure, is ground floor, the second layer, the 3rd layer and the 4th layer by beginning to count from substrate layer farthest.Wherein the ground floor of this film layer structure is the electrically conducting transparent surface, and this conductive layer has good electrical conductivity and resistance to marring, has used ITO, SiO
2, NbO and NbSiO be as Coating Materials.Disclosed film layer structure is:
This film layer structure also can reach high transmittance, and when visible wavelength was the 460nm-600nm scope, reflectivity can be lower than 0.1%.The thickness of same high refractive index layer is thicker, has increased the quantity of target and vacuum chamber, realizes that quantity-produced technology is complicated, the technology instability.
In sum, though existing techniques in realizing the combination of antireflection and conducting film, but in actual production, also exist problems such as cost height, technology instability, yield rate be low,, need provide new design proposal in order to solve the unsolved difficult problem of above-mentioned prior art.
Summary of the invention
The object of the present invention is to provide a kind of novel anti-reflection conductive film, had that cost is low, a process stabilizing, advantage that yield rate is high.
The object of the present invention is achieved like this:
Novel anti-reflection conductive film, described anti-reflection conductive film is attached on the transparent base (S), described anti-reflection conductive film is to include high refractive index layer (H) at least, low-index layer (L) and nesa coating (T), described high refractive index layer (H) refers to that wavelength is when 530nm-570nm, exponent of refractive index is at the film material of 2.1-2.4, described low-index layer (L) refers to that wavelength is when 530nm-570nm, exponent of refractive index is at the 1.4-1.5 film material, described nesa coating (T) refers to that wavelength is when 530nm-570nm, exponent of refractive index has the weak film material that absorbs at 1.85-1.95, and the structure of described anti-reflection conductive film is a kind of in following three kinds of membrane structures:
First kind of membrane structure is: the two sides at transparent base (S) outwards is followed successively by high refractive index layer (H) by close transparent base (S), low-index layer (L), and wherein Yi Mian outermost layer is nesa coating (T); The thickness of high refractive index layer (H) is between 5nm to 30nm, and the thickness of low-index layer (L) is between 60nm to 120nm, and the thickness of nesa coating (T) is between 5nm to 40nm, and the membrane structure of this spread pattern is recorded as the L/H/S/H/L/T type;
Second kind of membrane structure is: the two sides at transparent base (S) outwards is followed successively by high refractive index layer (H) by close transparent base (S), low-index layer (L), high refractive index layer (H), low-index layer (L), and the outermost layer in the one side of transparent base (S) is nesa coating (T), and the membrane structure of this spread pattern is recorded as (L/H)
2/ S/ (H/L)
2/ T type; The thickness of forming each rete of this 9 layers of composite membrane has following feature, at the thickness of the positive vertical outwards ground floor high refractive index layer (H) of the base material (S) of no nesa coating (T) at 5nm between the 30nm, the thickness of second layer low-index layer (L) at 5nm between the 40nm, the thickness of the 3rd floor height index layer (H) at 5nm between the 30nm, the thickness of the 4th layer of low-index layer (L) at 80nm between the 120nm; At the base material that nesa coating (T) arranged (S) back side thickness of vertical outwards ground floor high refractive index layer (H) at 5nm between the 30nm, the thickness of second layer low-index layer (L) at 5nm between the 40nm, the thickness of the 3rd floor height index layer (H) at 5nm between the 30nm, the thickness of the 4th layer of low-index layer (L) at 50nm between the 90nm, the thickness of layer 5 nesa coating (T) at 5nm between the 40nm; As shown in the table:
Also comprise middle index layer (M) in the arrangement architecture of the third film, described middle index layer (M) is meant wavelength when 530nm-570nm, and exponent of refractive index is at the film material of 1.6-1.7.The third membrane structure is characterised in that: the two sides at transparent base (S) outwards is followed successively by high refractive index layer (H) by close transparent base (S), middle index layer (M), and low-index layer (L), wherein Yi Mian outermost layer is nesa coating (T); The thickness of high refractive index layer (H) is between 5nm to 30nm, the thickness of low-index layer (L) is between 60nm to 120nm, the thickness of middle index layer (M) is between 5nm to 40nm, the thickness of nesa coating (T) is between 5nm to 40nm, and the membrane structure of this spread pattern is recorded as the L/M/H/S/H/M/L/T type.
Described transparent base (S) is glass or optical plastic, is transparent in wavelength 380nm-780nm scope, and its refractive index requires to be 1.40-1.70.
Described transparent base (S) is an optical glass, or polymethylmethacrylate (PMMA) or polycarbonate (PC) or poly terephthalic acid ethanol ester (PET), is transparent in wavelength 380nm-780nm scope, and its refractive index requires to be 1.40-1.70.
Described high refractive index layer (H) transparent nothing in wavelength 380nm-780nm scope absorbs, and its material is titania (TiO
2) or tantalum pentoxide (Ta
2O
5) or niobium pentaoxide (Nb
2O
5) or the oxide of niobium (Nb) tantalum (Ta) mixing back plated film formation or the oxide that titanium (Ti) niobium (Nb) mixes back plated film formation.
Described low-index layer (L) transparent nothing in wavelength 380nm-780nm scope absorbs, and its material can be monox (SiO
2) or silicon (Si) aluminium (Al) mix the oxide that the back plated film forms.
Its transparent nothing in wavelength 380nm-780nm scope of index layer (M) absorbs in described, and its material is aluminium oxide (Al
2O
3) or niobium (Nb) silicon (Si) mix the oxide that the back plated film forms.
Described nesa coating (T) is a kind of or potpourri between them in the following oxide, and described oxide is meant: tin indium oxide (ITO), tin oxide (SnO
2), zinc paste (ZnO), indium oxide (In
2O
3), fluorine doped tin oxide (SnO
2: F), mix arsenic tin oxide (SnO
2: Sb), Al-Doped ZnO (ZnO:Al), indium zinc oxide (In
2O
3: ZnO), zinc tin oxide (SnO
2: ZnO) and indium oxide magnesium (In
2O
3: MgO).
Described anti-reflection conductive film is to adopt the evaporation coating of batch production or continous way production or the composite membrane of the multi-layer film structure that the sputter coating system makes.
The invention provides three kinds of novel anti-reflection conductive films, anti-reflection conductive film is to include high refractive index layer (H), low-index layer (L), middle index layer (M) and nesa coating (T), high refractive index layer (H) is when wavelength 530nm-570nm, and exponent of refractive index is at the material TiO with maximum refractive index of 2.1-2.4
2, low-index layer (L) is when wavelength 530nm-570nm, and exponent of refractive index is at the SiO of 1.4-1.5
2, described nesa coating (T) refers to wavelength when 530nm-570nm, exponent of refractive index has the weak film material that absorbs at 1.85-1.95.The structure of three kinds of anti-reflection conductive films is L/H/S/H/L/T type, (L/H)
2/ S/ (H/L)
2/ T type and L/M/H/S/H/M/L/T type
The thickness of three kinds of structure high-index materials provided by the invention is less, can simplify technology, helps realizing the production of continuous batch.Simultaneously because large area display, cathode-ray tube (CRT) and touch-screen, be not only a photoelectric device, and be a decoration, so its appearance colour is had requirement, several colors that the present invention is directed to people's approval are carried out the optimization of rete, can realize the Color Range that people relatively approve by three kinds of structures that proposed.As: visual color is blue, light blue, redness and purple etc.
Description of drawings
Fig. 1 is the structural representation of the present invention's L/H/S/H/L/T type anti-reflection conductive film.
Fig. 2 is the present invention it (L/H)
2/ S/ (H/L)
2The structural representation of/T type anti-reflection conductive film.
Fig. 3 is the structural representation of the present invention's L/M/H/S/H/M/L/T type anti-reflection conductive film.
Fig. 4 is the stimulation functional arrangement of visible light to human eye.
Among the above-mentioned figure, H is a high refractive index layer, and L is a low-index layer, and M is middle index layer, and S is a substrate.
Specific embodiment
Embodiment 1: the present invention's L/H/S/H/L/T type anti-reflection conductive film
The concrete rete characteristics of the present invention's L/H/S/H/L/T type anti-reflection conductive film are:
High refractive index layer (H) is selected TiO for use
2, material is 2.1-2.4 at the exponent of refractive index of 530-570nm;
Low-index layer (L) is selected SiO for use
2, material is 1.4-1.5 at the exponent of refractive index of 530-570nm;
Baseplate material (S) is selected glass for use, and exponent of refractive index is 1.51-1.56 in visible-range;
Nesa coating (T) is selected ITO for use, and exponent of refractive index is between 1.85-1.95 in visible-range;
The Thickness Design of each layer is as follows:
With reference to figure 1, this rete reflection colour is light blue, and the reflectance value at 530nm-570nm wavelength place can reduce by 8.5% reflectivity on the reflectivity of original substrate.Because the thickness of high-index material is less, such thickness and film layer structure can reduce the cavity of vacuum continuous coating machine, and technology is simple, and easier realization is in enormous quantities produces continuously.Below for producing the typical process flow of this anti-reflection conductive film.
Rete of the present invention adopts continuous magnetron sputtering or evaporation to produce with batch sputter or evaporation, especially the method for continuous magnetron sputtering plated film.Adopt continuous magnetron sputtering method instantiation manufacturing step to be:
The continuous sputter coating process of glass needs through glass section, edging, chamfering, operations such as glass cleaning, plated film and detection.Plated film is implemented by following process program:
(1) the method sputter-coated glasses substrate of use direct current planar magnetron sputtering, employed target material is the Ti target during sputter, adopts and feeds Ar and O simultaneously at vacuum chamber
2Carry out the reactive sputtering plated film, form the TiO of high index of refraction
2Rete.Base plate glass is 60mm-120mm apart from target material surface, and to adopt well heater to keep the substrate temperature of this glass be 100 ℃-300 ℃, and the working pressure in the coating machine cavity is 0-10mTorr.
(2) use the method sputter-coated glasses substrate that exchanges the reaction planar magnetic control sputtering, the target material that uses during sputter is the Si target, adopts in the vacuum chamber and feeds Ar and O simultaneously
2Carry out the reactive sputtering plated film, form the SiO of low-refraction
2Rete.Base plate glass is 60mm-120mm apart from target material surface, and to adopt well heater to keep the substrate temperature of this glass be 100 ℃-300 ℃, and the working pressure in the coating machine cavity is 0-10mTorr.
(3) the method sputter-coated glasses substrate of use direct current or DC pulse magnetron sputtering, the material that uses during sputter is the ITO target, adopts at vacuum chamber feeding Ar and carries out sputter coating, forms the ITO rete.Base plate glass is 60mm-120mm apart from target material surface, and to adopt well heater to keep the substrate temperature of this glass be 100 ℃-300 ℃, and the working pressure in the coating machine cavity is 0-10mTorr.
(4) for realizing the technology of continuous sputter, need arrange the polylith target material simultaneously, peace cloth is coordinated many targets working stability technology simultaneously at different vacuum chambers.
Embodiment 2: the present invention it (L/H)
2/ S/ (H/L)
2/ T type anti-reflection conductive film
The present invention it (L/H)
2/ S/ (H/L)
2/ T type anti-reflection conductive film has 9 layers of structure, and the number of plies is more, but this structure can realize multiple color, thereby can adjust to needed color as required, and concrete rete characteristics are:
High refractive index layer (H) is selected TiO for use
2, material is 2.1-2.4 at the exponent of refractive index of 530-570nm;
Low-index layer (L) is selected SiO for use
2, material is 1.4-1.5 at the exponent of refractive index of 530-570nm;
Baseplate material (S) is selected glass for use, and exponent of refractive index is 1.51-1.56 in visible-range;
Nesa coating (T) is selected ITO for use, and exponent of refractive index is between 1.85-1.95 in visible-range;
The Thickness Design of each layer is as follows:
With reference to figure 2, this rete reflection colour is red, and the reflectance value at 530nm-570nm wavelength place can reduce by 8.8% reflectivity on the reflectivity of original substrate.Because the thickness of high-index material is less, technology is more stable, realizes continuous production in enormous quantities easily.
When the Thickness Design of each layer such as following table, this rete reflection colour is light blue, and the reflectance value at 530-570nm wavelength place can reduce by 8.8% reflectivity on the reflectivity of original substrate.
The typical process flow of anti-reflection conductive film and first kind of film layer structure example are roughly the same, the glass section are all arranged, edging, chamfering, operations such as glass cleaning, plated film and detection.Difference is the layout of vacuum coating target material and the layout of vacuum cavity.
Embodiment 3: the present invention's L/M/H/S/H/M/L/T type anti-reflection conductive film
Many index layers (M) in one deck in the present invention's the L/M/H/S/H/M/L/T type anti-reflection conductive film structure, this structure can realize more stable technology, concrete rete characteristics are:
High refractive index layer (H) is selected TiO for use
2, material is 2.1-2.4 at the exponent of refractive index of 530nm-570nm;
Middle index layer (M), material is when 530nm-570nm, and exponent of refractive index is at 1.6-1.7;
Low-index layer (L) is selected SiO for use
2, material is 1.4-1.5 at the exponent of refractive index of 530-570nm;
Baseplate material (S) is selected glass for use, and exponent of refractive index is 1.51-1.56 in visible-range;
Nesa coating (T) is selected ITO for use, and exponent of refractive index is between 1.85-1.95 in visible-range;
The Thickness Design of each layer is as follows
With reference to figure 3, this rete reflection colour is blue, and the reflectance value at 530nm-570nm wavelength place can reduce by 8.6% reflectivity on the reflectivity of original substrate.Because the thickness of high refractive index layer and middle index layer is less, technology is more stable, realizes continuous production in enormous quantities easily.
Three kinds of membrane structures provided by the invention can specifically be adjusted in the thickness range of claim, obtain needed color and specific antireflection requirement.Three kinds of structures of the present invention have at first broken through prior art because rete is thicker, and the filming equipment that causes is huge, and the shortcoming of complex process has been simplified film layer structure; Secondly, film layer structure of the present invention is being considered under the antireflecting effect of vision, can adjust the film layer structure acquisition different color of anti-reflective film according to different needs; Moreover the material that the present invention uses is general film material, and technology is simple, realizes continuous production in enormous quantities easily.
Should be noted that herein openly can replace with the identical structure of other effect that the embodiment that the present invention introduced simultaneously realizes unique structure of the present invention with the structure of explanation.Though preferential embodiment of the present invention is introduced in this article and is illustrated; but those skilled in the art know and know that these embodiment illustrate; those skilled in the art can make countless variations, improvement and replacement; and can not break away from the present invention; therefore, should be according to the next qualification protection scope of the present invention of the spirit and scope of appending claims of the present invention.